Italy
Solid State Hydrogen Storage in Alanates and Alanate-Based Compounds: A Review
Jul 2018
Publication
The safest way to store hydrogen is in solid form physically entrapped in molecular form in highly porous materials or chemically bound in atomic form in hydrides. Among the different families of these compounds alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997 when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li Na K Ca Mg Y Eu and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performance.
Energy Saving in Public Transport Using Renewable Energy
Jan 2017
Publication
Hydrogen produced by renewable sources represents an interesting way to reduce the energetic dependence on fossil fuels in the transportation sector. This paper shows a feasibility study for the production storage and distribution of hydrogen in the western Sicilian context using three different renewable sources: wind biomass and sea wave. The objective of this study is the evaluation of the hydrogen demand needed to replace all diesel supplied buses with electrical buses equipped with fuel cells. An economic analysis is presented with the evaluation of the avoidable greenhouse gas emissions. Four different scenarios correlate the hydrogen demand for urban transport to the renewable energy resources present in the territories and to the modern technologies available for the production of hydrogen. The study focuses on the possibility of tapping into the potential of renewable energies (wind biomass and sea wave) for the production of hydrogen by electrolysis. The use of hydrogen would reduce significantly the emissions of particulate and greenhouse gases in the urban districts under analysis.
Willingness to Pay and Public Acceptance for Hydrogen Buses: A Case Study of Perugia
Sep 2015
Publication
Sustainability transportation is characterized by a positive externality on the environment health social security land use and social inclusion. The increasing interest in global warming has caused attention to be paid to the introduction of the hydrogen bus (H2B). When introducing new environmental technologies such as H2B it is often necessary to assess the environmental benefits related to this new technology. However such benefits are typically non-priced due to their public good nature. Therefore we have to address this problem using the contingent valuation (CV) method. This method has been developed within environmental economics as a means to economically assess environmental changes which are typically not traded in the market. So far several big cities have been analyzed to evaluate the perceived benefit related to H2B introduction but to the best of our knowledge no one has performed a CV analysis of a historical city where smog also damages historical buildings. This paper presents the results obtained using a multi-wave survey. We have investigated user preferences to elicit their willingness to pay for H2B introduction in Perugia taking into account all types of negative externalities due to the traffic pollution. The results confirm that residents in Perugia are willing to pay extra to support the introduction of H2B.
Optimal Integration of Hydrogen-Based Energy Storage Systems in Photovoltaic Microgrids: A Techno-Economic Assessment
Aug 2020
Publication
The feasibility and cost-effectiveness of hydrogen-based microgrids in facilities such as public buildings and small- and medium-sized enterprises provided by photovoltaic (PV) plants and characterized by low electric demand during weekends were investigated in this paper. Starting from the experience of the microgrid being built at the Renewable Energy Facility of Sardegna Ricerche (Italy) which among various energy production and storage systems includes a hydrogen storage system a modeling of the hydrogen-based microgrid was developed. The model was used to analyze the expected performance of the microgrid considering different load profiles and equipment sizes. Finally the microgrid cost-effectiveness was evaluated using a preliminary economic analysis. The results demonstrate that an effective design can be achieved with a PV system sized for an annual energy production 20% higher than the annual energy requested by the user and a hydrogen generator size 60% of the PV nominal power size. This configuration leads to a self-sufficiency rate of about 80% and without public grants a levelized cost of energy comparable with the cost of electricity in Italy can be achieved with a reduction of at least 25–40% of the current initial costs charged for the whole plant depending on the load profile shape.
Thermal Efficiency of On-site, Small-scale Hydrogen Production Technologies using Liquid Hydrocarbon Fuels in Comparison to Electrolysis a Case Study in Norway
Oct 2018
Publication
The main goal of this study was to assess the energy efficiency of a small-scale on-site hydrogen production and dispensing plant for transport applications. The selected location was the city of Narvik in northern Norway where the hydrogen demand is expected to be 100 kg/day. The investigated technologies for on-site hydrogen generation starting from common liquid fossil fuels such as heavy naphtha and diesel were based on steam reforming and partial oxidation. Water electrolysis derived by renewable energy was also included in the comparison. The overall thermal efficiency of the hydrogen station was computed including compression and miscellaneous power consumption.
Analysis of the Existing Barriers for the Market Development of Power to Hydrogen (P2H) in Italy
Sep 2020
Publication
New technological solutions are required to control the impact of the increasing presence of renewable energy sources connected to the electric grid that are characterized by unpredictable production (i.e. wind and solar energy). Energy storage is becoming essential to stabilize the grid when a mismatch between production and demand occurs. Among the available solutions Power to Hydrogen (P2H) is one of the most attractive options. However despite the potential many barriers currently hinder P2H market development. The literature reports general barriers and strategies to overcome them but a specific analysis is fundamental to identifying how these barriers concretely arise in national and regional frameworks since tailored solutions are needed to foster the development of P2H local market. The paper aims to identify and to analyze the existing barriers for P2H market uptake in Italy. The paper shows how several technical regulatory and economic issues are still unsolved resulting in a source of uncertainty for P2H investment. The paper also suggests possible approaches and solutions to address the Italian barriers and to support politics and decision-makers in the definition and implementation of the national hydrogen strategy.
Risk Analysis of the Storage Unit in Hydrogen Refuelling Station
Sep 2007
Publication
Nowadays consumer demand for local and global environmental quality in terms of air pollution and in particular greenhouse gas emissions reduction may help to drive to the introduction of zero emission vehicles. At this regard the hydrogen technology appears to have future market valuablepotential. On the other hand the use of hydrogen vehicles which requires appropriate infrastructures for production storage and refuelling stages presents a lot of safety problems due to the peculiar chemicophysical hydrogen characteristics. Therefore safe at the most practices are essential for the successful proliferation of hydrogen vehicles. Indeed to avoid limit hazards it is necessary to implement practices that if early adopted in the development of a fuelling station project can allow very low environmental impact safety being incorporated in the project itself. Such practices generally consist in the integrated use of Failure Mode and Effect Analysis (FMEA) HAZard OPerability (HAZOP) and Fault Tree Analysis (FTA) which constitute well established standards in reliability engineering. At this regard however a drawback is the lack of experience and the scarcity of the relevant data collection. In this work we present the results obtained by the integrated use of FMEA HAZOP and FTA analyses relevant for the moment the high-pressure storage equipment in a hydrogen gas refuelling station. The study that is intended to obtain elements for improving safety of the system can constitute a basis for further more refined works.
Macroeconomic Factors Influencing Public Policy Strategies for Blue and Green Hydrogen
Nov 2021
Publication
The aim of this paper is to analyze the factors affecting hydrogen and Carbon Capture and Storage Technologies (“CCS”) policies taking into consideration Fossil Fuel Consumption Oil Reserves the Debt/GDP Ratio the Trilemma Index and other variables with respect to OECD countries. STATA 17 was used for the analysis. The results confirm the hypothesis that countries with high fossil fuel consumption and oil reserves are investing in blue hydrogen and CCS towards a “zero-carbon-emission” perspective. Moreover countries with a good Debt/GDP ratio act most favorably to green policies by raising their Public Debt because Foreign Direct Investments are negatively correlated with those kinds of policies. Future research should exploit Green Finance policy decision criteria on green and blue hydrogen.
Innovative Passive Protection Systems For Hydrogen Production Plants
Sep 2005
Publication
As a part of a broader project on hydrogen production by reforming of methane in a membrane catalytic reactor this paper outlines the research activity performed at the University of Pisa Department of Chemical Engineering aimed at developing and testing composite panels that can operate as thermal protective shields against hydrogen jet fires. The shield design criterion that appears to give a more practical and convenient solution for the type of installation to be protected is the one that suggest to realize composite panels. Composite material are made of two elements fiber and matrix. In this study composite panels will be realized with basalt fabric as fiber and epoxy-phenolic resins as matrix. Therefore following the indications given by norms as UNI 9174 and ASTM E 1321-93 a test method has been studied to obtain temperature data from a specimen impinged by an hydrogen flame. Thanks to thermocouples applied on backside of the sample and an infrared video camera to realize thermal images of specimen surface impinged by flame this type of test try to characterize the behaviour of composite materials under the action of hydrogen flame simulating in a simple way the action of hydrogen jet fires.
Evaluation of Sorbents for High Temperature Removal of Tars, Hydrogen Sulphide, Hydrogen Chloride and Ammonia from Biomass-derived Syngas by Using Aspen Plus
Jan 2020
Publication
Biomass gasification is a promising technology to produce secondary fuels or heat and power offering considerable advantages over fossil fuels. An important aspect in the usage of producer gas is the removal of harmful contaminants from the raw syngas. Thus the object of this study is the development of a simulation model for a gasifier including gas clean-up for which a fluidized-bed gasifier for biomass-derived syngas production was considered based on a quasi-equilibrium approach through Gibbs free energy minimisation and including an innovative hot gas cleaning constituted by a combination of catalyst sorbents inside the gasification reactor catalysts in the freeboard and subsequent sorbent reactors by using Aspen Plus software. The gas cleaning chain simulates the raw syngas clean-up for several organic and inorganic contaminants i.e. toluene benzene naphthalene hydrogen sulphide hydrogen chloride and ammonia. The tar and inorganic contaminants final values achieved are under 1 g/Nm3 and 1 ppm respectively.
Safety Distances- Definition and Values
Sep 2005
Publication
In order to facilitate the introduction of a new technology as it is the utilization of hydrogen as an energy carrier development of safety codes and standards besides the conduction of demonstrative projects becomes a very important action to be realized. Useful tools of work could be the existing gaseous fuel codes (natural gas and propane) regulating the stationary and automotive applications. Some safety codes have been updated to include hydrogen but they have been based on criteria and/or data applicable for large industrial facilities making the realization of public hydrogen infrastructures prohibitive in terms of space. In order to solve the above mentioned problems others questions come out: how these safety distances have been defined? Which hazard events have been taken as reference for calculation? Is it possible to reduce the safety distances through an appropriate design of systems and components or through the predisposition of adequate mitigation measures? This paper presents an analysis of the definitions of “safety distances” and “hazardous locations” as well as a synoptic analysis of the different values in force in several States for hydrogen and natural gas. The above mentioned synoptic table will highlight the lacks and so some fields that need to be investigated in order to produce a suitable hydrogen standard.
Low-carbon Hydrogen Via Integration of Steam Methane Reforming with Molten Carbonate Fuel Cells at Low Fuel Utilization
Feb 2021
Publication
Hydrogen production is critical to many modern chemical processes – ammonia synthesis petroleum refining direct reduction of iron and more. Conventional approaches to hydrogen manufacture include steam methane reforming and autothermal reforming which today account for the lion's share of hydrogen generation. Without CO2 capture these processes emit about 8.7 kg of CO2 for each kg of H2 produced. In this study a molten carbonate fuel cell system with CO2 capture is proposed to retrofit the flue gas stream of an existing Steam Methane Reforming plant rated at 100000 Nm3 h−1 of 99.5% pure H2. The thermodynamic analysis shows direct CO2 emissions can be reduced by more than 95% to 0.4 to 0.5 kg CO2 /kg H2 while producing 17% more hydrogen (with an increase in natural gas input of approximately 37%). Because of the additional power and hydrogen generation of the carbonate fuel cell the efficiency debit associated with CO2 capture is quite small reducing the SMR efficiency from 76.6% without capture to 75.6% with capture. In comparison the use of standard amine technology for CO2 capture reduces the efficiency below 70%. This demonstrates the synergistic nature of the carbonate fuel cells which can reform natural gas to H2 while simultaneously capturing CO2 from the SMR flue gas and producing electricity giving rise to a total system with very low emissions yet high efficiency.
Control of Electrons’ Spin Eliminates Hydrogen Peroxide Formation During Water Splitting
Jul 2017
Publication
The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed while the overall current through the cell correlating with the water splitting process is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements in which chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way toward better chiral dye-sensitized photoelectrochemical cells.
European Hydrogen Safety Training Programme for First Responders: Hyresponse Outcomes and Perspectives
Sep 2017
Publication
The paper presents the outcomes of the HyResponse project i.e. the European Hydrogen Safety Training Programme for first responders. The threefold training is described: the content of the educational training is presented the operational training platform and its mock-up real scale transport and hydrogen stationary installations are detailed and the innovative virtual tools and training exercises are highlighted. The paper underlines the outcomes the three pilot sessions as well as the Emergency Response Guide available on the HyResponse’s public website. The next steps for widespread dissemination into the community are discussed.
Life Cycle Performance of Hydrogen Production via Agro-Industrial Residue Gasification—A Small Scale Power Plant Study
Mar 2018
Publication
This study evaluates the environmental profile of a real biomass-based hydrogen production small-scale (1 MWth) system composed of catalytic candle indirectly heated steam gasifier coupled with zinc oxide (ZnO) guard bed water gas shift (WGS) and pressure swing absorber (PSA) reactors. Environmental performance from cradle-to-gate was investigated by life cycle assessment (LCA) methodology. Biomass production shows high influence over all impact categories. In the syngas production process the main impacts observed are global warming potential (GWP) and acidification potential (AP). Flue gas emission from gasifier burner has the largest proportion of total GWP. The residual off gas use in internal combustion engine (ICE) leads to important environmental savings for all categories. Hydrogen renewability score is computed as 90% due to over 100% decline in non-renewable energy demand. Sensitivity analysis shows that increase in hydrogen production efficiency does not necessarily result in decrease in environmental impacts. In addition economic allocation of environmental charges increases all impact categories especially AP and photochemical oxidation (POFP).
Mixing of Dense or Light Gases with Turbulent Air- a Fast-Running Model for Lumped Parameter Codes
Sep 2005
Publication
The release of gases heavier than air like propane at ground level or lighter than air like hydrogen close to a ceiling can both lead to fire and explosion hazards that must be carefully considered in safety analyses. Even if the simulation of accident scenarios in complex installations and long transients often appears feasible only using lumped parameter computer codes the phenomenon of denser or lighter gas dispersion is not implicitly accounted by these kind of tools. In the aim to set up an ad hoc model to be used in the computer code ECART fluid-dynamic simulations by the commercial FLUENT 6.0 CFD code are used. The reference geometry is related to cavities having variable depth (2 to 4 m) inside long tunnels filled with a gas heavier or lighter than air (propane or hydrogen). Three different geometrical configurations with a cavity width of 3 6 and 9 m are considered imposing different horizontal air stream velocities ranging from 1 to 5 m/s. A stably-stratified flow region is observed inside the cavity during gas shearing. In particular it is found that the density gradient tends to inhibit turbulent mixing thus reducing the dispersion rate. The obtained data are correlated in terms of main dimensionless groups by means of a least squares method. In particular the Sherwood number is correlated as a function of Reynolds a density ratio modified Froude numbers and in terms of the geometrical parameter obtained as a ratio between the depth of the air-dense gas interface and the length of the cavity. This correlation is implemented in the ECART code to add the possibility to simulate large installations during complex transients lasting many hours with reasonable computation time. An example of application to a typical case is presented.
Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage
Apr 2018
Publication
Hydrogen storage in the solid state represents one of the most attractive and challenging ways to supply hydrogen to a proton exchange membrane (PEM) fuel cell. Although in the last 15 years a large variety of material systems have been identified as possible candidates for storing hydrogen further efforts have to be made in the development of systems which meet the strict targets of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and U.S. Department of Energy (DOE). Recent projections indicate that a system possessing: (i) an ideal enthalpy in the range of 20–50 kJ/mol H2 to use the heat produced by PEM fuel cell for providing the energy necessary for desorption; (ii) a gravimetric hydrogen density of 5 wt. % H2 and (iii) fast sorption kinetics below 110 ◦C is strongly recommended. Among the known hydrogen storage materials amide and imide-based mixtures represent the most promising class of compounds for on-board applications; however some barriers still have to be overcome before considering this class of material mature for real applications. In this review the most relevant progresses made in the recent years as well as the kinetic and thermodynamic properties experimentally measured for the most promising systems are reported and properly discussed.
A Preliminary Assessment of the Potential of Low Percentage Green Hydrogen Blending in the Italian Natural Gas Network
Oct 2020
Publication
The growing rate of electricity generation from renewables is leading to new operational and management issues on the power grid because the electricity generated exceeds local requirements and the transportation or storage capacities are inadequate. An interesting option that is under investigation by several years is the opportunity to use the renewable electricity surplus to power electrolyzers that split water into its component parts with the hydrogen being directly injected into natural gas pipelines for both storage and transportation. This innovative approach merges together the concepts of (i) renewable power-to-hydrogen (P2H) and of (ii) hydrogen blending into natural gas networks. The combination of renewable P2H and hydrogen blending into natural gas networks has a huge potential in terms of environmental and social benefits but it is still facing several barriers that are technological economic legislative. In the framework of the new hydrogen strategy for a climate-neutral Europe Member States should design a roadmap moving towards a hydrogen ecosystem by 2050. The blending of “green hydrogen” that is hydrogen produced by renewable sources in the natural gas network at a limited percentage is a key element to enable hydrogen production in a preliminary and transitional phase. Therefore it is urgent to evaluate at the same time (i) the potential of green hydrogen blending at low percentage (up to 10%) and (ii) the maximum P2H capacity compatible with low percentage blending. The paper aims to preliminary assess the green hydrogen blending potential into the Italian natural gas network as a tool for policy makers grid and networks managers and energy planners.
Design and Costs Analysis of Hydrogen Refuelling Stations Based on Different Hydrogen Sources and Plant Configurations
Jan 2022
Publication
In this study the authors present a techno-economic assessment of on-site hydrogen refuelling stations (450 kg/day of H2 ) based on different hydrogen sources and production technologies. Green ammonia biogas and water have been considered as hydrogen sources while cracking autothermal reforming and electrolysis have been selected as the hydrogen production technologies. The electric energy requirements of the hydrogen refuelling stations (HRSs) are internally satisfied using the fuel cell technology as power units for ammonia and biogas-based configurations and the PV grid-connected power plant for the water-based one. The hydrogen purification where necessary is performed by means of a Palladium-based membrane unit. Finally the same hydrogen compression storage and distribution section are considered for all configurations. The sizing and the energy analysis of the proposed configurations have been carried out by simulation models adequately developed. Moreover the economic feasibility has been performed by applying the life cycle cost analysis. The ammonia-based configurations are the best solutions in terms of hydrogen production energy efficiency (>71% LHV) as well as from the economic point of view showing a levelized cost of hydrogen (LCOH) in the range of 6.28 EUR/kg to 6.89 EUR/kg a profitability index greater than 3.5 and a Discounted Pay Back Time less than five years.
Seasonal Energy Storage for Zero-emissions Multi-energy Systems Via Underground Hydrogen Storage
Jan 2020
Publication
The deployment of diverse energy storage technologies with the combination of daily weekly and seasonal storage dynamics allows for the reduction of carbon dioxide (CO2) emissions per unit energy provided. In particular the production storage and re-utilization of hydrogen starting from renewable energy has proven to be one of the most promising solutions for offsetting seasonal mismatch between energy generation and consumption. A realistic possibility for large-scale hydrogen storage suitable for long-term storage dynamics is presented by salt caverns. In this contribution we provide a framework for modelling underground hydrogen storage with a focus on salt caverns and we evaluate its potential for reducing the CO2 emissions within an integrated energy systems context. To this end we develop a first-principle model which accounts for the transport phenomena within the rock and describes the dynamics of the stored energy when injecting and withdrawing hydrogen. Then we derive a linear reduced order model that can be used for mixed-integer linear program optimization while retaining an accurate description of the storage dynamics under a variety of operating conditions. Using this new framework we determine the minimum-emissions design and operation of a multi-energy system with H2 storage. Ultimately we assess the potential of hydrogen storage for reducing CO2 emissions when different capacities for renewable energy production and energy storage are available mapping emissions regions on a plane defined by storage capacity and renewable generation. We extend the analysis for solar- and wind-based energy generation and for different energy demands representing typical profiles of electrical and thermal demands and different CO2 emissions associated with the electric grid.
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